Organic silicon modified dry-process paper for oil-water separation and preparation method of organic silicon modified dry-process paper

Abstract

The invention belongs to the field of oil-water separation treatment, and particularly discloses organic silicon modified dry paper for oil-water separation and a preparation method thereof.The preparation method comprises the following steps that alkyl chain organosiloxane and a cationic photoinitiator are mixed and stirred to be uniform in a dark place at the room temperature, and photosensitive organic silicon mixed liquid is obtained; and adding the prepared photosensitive organic silicon mixed solution into a spray gun, uniformly spraying on dry paper, and carrying out photopolymerization to obtain the organic silicon modified dry paper for oil-water separation. According to the invention, the organopolysiloxane obtained through hydrolytic polycondensation is of a three-dimensional network structure and has excellent wear resistance and solvent resistance, and by combining good tensile strength and large aperture of the substrate dry-process fiber paper, the oil-water separation paper has excellent oil-water separation performance and can be repeatedly used for more than 50 times; the raw materials are simple, the cost is low, and the base material can be degraded and regenerated and is green and environment-friendly; the preparation process is simple, the used time is short, no organic solvent is used, and the pollution is less; and the method is suitable for large-scale production and application.

Description

Technical Field

[0001] The invention relates to the field of oil-water separation processing, and in particular to an organosilicon-modified dry-laid paper for oil-water separation and a preparation method thereof. Background Art

[0002] With the continuous development of social economy, the sewage generated and discharged in human production and life is increasing. These sewage are often a mixture of water and oil, and the oil-containing components are generally toxic. If not handled properly, they will cause serious harm to local water bodies. In addition, offshore crude oil spills caused by human activities will also seriously threaten the marine environment and the life safety of organisms. Faced with the increasingly serious oil pollution problem, researchers have developed a series of oil-water separation methods. For example: adsorption method, combustion method, flocculant method, microbial degradation method and other oil-water separation methods. However, the above methods are often not used alone, but more often multiple separation methods are superimposed. There are disadvantages such as long separation time, low efficiency, large area, difficulty in technical superposition, and easy to cause secondary pollution.

[0003] Super-hydrophobic materials have important applications in many fields such as anti-corrosion, lubrication, and waterproofing, which have aroused great interest among scientists. Researchers have realized the super-hydrophobic properties of substrate materials by the method of impregnating hydrophobic solution modification with porous metal mesh or fiber fabric as substrate, and obtained super-hydrophobic oil-water separation materials. Although the super-hydrophobic material oil-water separation effect prepared by this method is excellent, there are still deficiencies such as low number of reuses and poor solvent resistance, and the substrate material used is a non-degradable material. Therefore, selecting degradable materials to prepare oil-water separation materials not only meets the needs of environmental protection, but also meets the requirements of cost.

[0004] Cellulose is a renewable biomaterial with good mechanical properties, flexibility, air permeability and recyclability. The dry-laid paper made of cellulose as raw material can meet the demand while maintaining a low production cost. Cellulose macromolecules contain a large number of hydroxyl groups, which makes it a hydrophilic material, but also facilitates the hydrophobic modification of cellulose. Chinese patent CN 113186756A discloses a method for preparing super-hydrophobic cellulose paper for oil-water separation. The prepared super-hydrophobic material for oil-water separation has the advantages of wear resistance, high strength, solvent resistance, acid and alkali resistance, etc. The prepared material has the characteristics of cheapness and greenness, but its preparation process is complicated, the drying and aging temperature is high, and the reaction conditions are harsh, which limits its promotion and application. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing silicone-modified dry-laid paper for oil-water separation. The raw material pollution of the present invention is small, the cost is low, the preparation process is simple, the time is short, and the reaction conditions are easy to achieve, which can effectively solve the problems in the background technology.

[0006] The present invention is achieved through the following technical solutions: A method for preparing organosilicon-modified dry-laid paper for oil-water separation comprises the following steps: S1: Mix an alkyl chain organosiloxane with a cationic photoinitiator, stir evenly at room temperature in the dark, and obtain a photosensitive organosilicon mixed liquid; S2: Take the prepared photosensitive organosilicon mixed liquid and add it to a spray gun, spray it evenly on dry-laid paper, polymerize it under light, and obtain organosilicon-modified dry-laid paper for oil-water separation.

[0007] A further improvement of the present invention is: In S1, the mass ratio of the alkyl chain organosiloxane to the cationic photoinitiator is 100:2-12.

[0008] Furthermore, the alkyl chain organosiloxane is one or a mixture of two or more of dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane.

[0009] Furthermore, the cationic photoinitiator is one or a mixture of two of bis(dodecylphenyl)iodine hexafluoroantimonate (UV1242) and 2-methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thienylethylene-phenylacetonitrile (PAG103).

[0010] Furthermore, in S2, the air-laid paper is air-formed air-laid fiber paper.

[0011] Furthermore, in S2, the spraying amount of the photosensitive silicone mixture is 10-300 g / m 2 .

[0012] Furthermore, in S2, the light source used in the photopolymerization process is a mercury lamp with a light intensity of 20-500 mW / cm 2 .

[0013] Furthermore, in S1, the time of stirring in the dark is 60-120 min; and in S2, the time of photopolymerization is 10-60 min.

[0014] A further improvement of the present invention is: A kind of organic silicon modified dry-process paper for oil-water separation is prepared by the above preparation method. Beneficial Effects

[0015] Compared with the prior art, the present invention has the following obvious advantages: 1. The present invention uses air-formed dry-laid fiber paper as a substrate, and polymerizes and modifies alkyl chain organosiloxane on the fiber paper surface through a hydrolysis and polycondensation reaction initiated by cations to prepare organosilicon-modified dry-laid paper for oil-water separation. The organopolysiloxane material formed by the hydrolysis and polycondensation reaction is a three-dimensional network structure with excellent wear resistance and solvent resistance. Combined with the good tensile strength and large pore size of the dry-laid fiber paper, the prepared modified fiber paper has excellent oil-water separation performance and can be reused for more than 50 times.

[0016] 2. The raw materials of the present invention are simple and low in cost. Only alkyl chain organic siloxane, a small amount of cationic photoinitiator and base material dry-process fiber paper are used. The dry-process fiber paper is degradable, renewable and green. The preparation process is simple and short in time. No organic solvent is used and the pollution is small. The reaction conditions are easy to achieve. The polymerization reaction only needs to be carried out under light at room temperature, which is suitable for large-scale production applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The following are scanning electron microscope (SEM) photos of dry-laid fiber paper before and after modification, wherein (a) is the dry-laid fiber paper before modification, and (b) is the dry-laid fiber paper after modification according to Example 2. DETAILED DESCRIPTION

[0018] The present invention is further described in detail below in conjunction with embodiments, but the embodiments of the present invention are not limited thereto. Example 1

[0019] At room temperature, take 35g of octadecyltrimethoxysilane (C18TMS) and 4.2g of cationic photoinitiator bis(dodecylphenyl)iodine hexafluoroantimonate (UV1242) into a brown screw-mouth bottle, and stir for 120 min after light shielding. Use a spray gun to evenly spray the mixed photosensitive silicone mixture on the dry fiber paper at a spraying amount of 100g / m², and then place it under a light intensity of 100mW / cm 2 The paper was irradiated under a mercury lamp for 30 min to obtain organosilicon-modified dry-process paper. Example 2

[0020] At room temperature, take 35g of hexadecyltrimethoxysilane (C16TMS) and 3.5g of cationic photoinitiator bis(dodecylphenyl)iodine hexafluoroantimonate (UV1242) into a brown screw-mouth bottle, shield it from light and stir for 80 minutes. Use a spray gun to evenly spray the mixed photosensitive silicone mixture on the dry fiber paper at a spraying amount of 150g / m², and then place it under a light intensity of 100mW / cm 2 The paper was irradiated under a mercury lamp for 30 min to obtain organosilicon-modified dry-process paper. Example 3

[0021] At room temperature, take 35g of dodecyltrimethoxysilane (C12TMS) and 2.4g of cationic photoinitiator bis(dodecylphenyl)iodine hexafluoroantimonate (UV1242) into a brown screw-mouth bottle, shield it from light and stir for 60 minutes. Use a spray gun to evenly spray the mixed photosensitive silicone mixture on the dry fiber paper at a spraying amount of 300g / m², and then place it under a light intensity of 200mW / cm 2 The obtained paper was irradiated under a mercury lamp for 60 min to obtain organosilicon-modified dry-process paper. Example 4

[0022] At room temperature, take 35g of 1H,1H,2H,2H-perfluorooctyl trimethoxysilane and 3g of cationic photoinitiator 2-methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thienylmethyl-phenylacetonitrile (PAG103) into a brown screw-mouth bottle, shield it from light and stir for 60 minutes. Use a spray gun to evenly spray the mixed photosensitive silicone mixture on the dry fiber paper at a spraying amount of 150g / m², and then place it under light intensity of 100mW / cm 2 The paper was irradiated under a mercury lamp for 30 min to obtain organosilicon-modified dry-process paper. Example 5

[0023] At room temperature, 35g of octadecyltrimethoxysilane (C18TMS) and 1.5g of cationic photoinitiator 2-methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thienylmethyl-phenylacetonitrile (PAG103) were placed in a brown screw-mouth bottle, and stirred for 60 minutes after light shielding. The mixed photosensitive silicone mixture was evenly sprayed on the dry fiber paper using a spray gun at a spraying amount of 40g / m², and then placed under a light intensity of 100mW / cm 2 The paper was irradiated under a mercury lamp for 10 min to obtain organosilicon-modified dry-process paper. Example 6

[0024] At room temperature, take 35g of octadecyltrimethoxysilane (C18TMS) and 1g of cationic photoinitiator (bis(dodecylphenyl)iodine hexafluoroantimonate) (UV1242) into a brown screw-mouth bottle, and stir for 60 minutes after light shielding. Use a spray gun to evenly spray the mixed photosensitive silicone mixture on the dry fiber paper at a spraying amount of 100g / m², and then place it under light intensity of 20mW / cm 2 The obtained paper was irradiated under a mercury lamp for 60 min to obtain organosilicon-modified dry-process paper.

[0025] The test description of Examples 1 to 6 specifically includes the tests of hydrophobicity, separation flux, first separation efficiency, and separation efficiency after 50 times, as shown in Table 1.

[0026] Table 1 Performance test results of organosilicon modified dry-laid paper prepared in different embodiments

[0027] As can be seen from Table 1, the water contact angles of the embodiments of the present invention are all above 135°, with high hydrophobic properties, and the first separation efficiency can reach above 96%. In the embodiments, as the amount of photosensitive organic silicon mixed liquid sprayed increases, the separation flux of the sample decreases. After repeating the oil-water separation 50 times, the photosensitive organic silicon mixed liquid with a high spray amount can still maintain a good separation effect, and has strong repeatability and practicality.

[0028] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing organosilicon-modified dry-laid paper for oil-water separation, characterized in that: The following steps are involved: S1: Mixing an alkyl chain organosiloxane and a cationic photoinitiator, stirring evenly at room temperature in the dark, to obtain a photosensitive organosilicone mixture; S2: Take the photosensitive organic silicon mixed liquid prepared above and add it to a spray gun, spray it evenly on the dry-laid paper, and polymerize it under light to obtain organic silicon-modified dry-laid paper for oil-water separation.

2. The method for preparing a silicone-modified dry-laid paper for oil-water separation according to claim 1, characterized in that: In S1, the mass ratio of the alkyl chain organosiloxane to the cationic photoinitiator is 100:2-12.

3. The method for preparing a silicone-modified dry-laid paper for oil-water separation according to claim 1 or 2, characterized in that: The alkyl chain organosiloxane is one or a mixture of two or more of dodecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane.

4. The method for preparing a silicone-modified dry-laid paper for oil-water separation according to claim 1 or 2, characterized in that: The cationic photoinitiator is one or a mixture of bis(dodecylphenyl)iodine hexafluoroantimonate (UV1242) and 2-methyl-α-[2-[[propanesulfonyl]imide]-3(2H)-thienylethylene-phenylacetonitrile (PAG103).

5. The method for preparing a silicone-modified dry-laid paper for oil-water separation according to claim 1, characterized in that: In S2, the air-laid paper is air-formed air-laid fiber paper.

6. The method for preparing a silicone-modified dry-laid paper for oil-water separation according to claim 1, characterized in that: In S2, the spraying amount of the photosensitive silicone mixture is 10-300 g / m 2 .

7. The method for preparing a silicone-modified dry-laid paper for oil-water separation according to claim 1, characterized in that: In S2, the light source used in the photopolymerization process is a mercury lamp with a light intensity of 20-500 mW / cm 2 .

8. The method for preparing a silicone-modified dry-laid paper for oil-water separation according to claim 1, characterized in that: In S1, the light-shielded stirring time is 60-120 min; and in S2, the light-induced polymerization time is 10-60 min.

9. An organosilicon-modified dry-laid paper for oil-water separation prepared by the preparation method according to any one of claims 1 to 8.

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